Amino arylated amino naphthalene derivatives



firsame.

Patented May 10, 1932 HEINRICH} AND PAUL I TO GENERAL ANILINE worms; DELAWARE s 7 Aivrmo' ARYLATED Amino NAPHTHALENE DERIVATIVES- No Drawing. Application filedllToveinber 15, 1e29,

Qur present invention relates to new amin'onaphthalene derivatives substituted inthe amino-group by an amino benzene compound and to a process of manufacturmg "Further-"details may beseen from the specification following hereafter;

In- German Letters" Patents Nos. 122,570,

1255589, and Zeitshrift fiir Farbenund.

IO'Textil Ohemie 1 904,page57 et seq=,-h'as been described the production of arylated amino naphthalene derivatives by treating aminonaphthalenes or primary amino-aryLcompounds of the ben- 1 zene series in the'presence of a sodium bisulfite solution. It is stated therein: that this reaction runs smoothly and gives satisfactory yields of the productsdesired when usingi'as" one component ammonaphthalene I or hy-droxynaphthalene compounds containingin their molecule sulfuric acid or carboxyhc.

acid groups. But When usingaaminonaphthalenes or hydro-Xynaphthalenes not substi- M tuted by sulfuric acid or carboxlylic acid groups the yield is very unsatisfactory (see Zeitschrift Farb'ene und Textil Ghemie 1904.,1pa e' 5s, and Chemie II, 75, page 252) p I In contrad'istinction 'to We have foundfthat" arylated compounds of aminonaphthalenes maybe obtained corresponding, to the general formula C H Y (NHU H 'XQ tk 'wherein Y stands forH or"aunivalent' substituent except the groups COOH, SO3H and wherein V a R v N R' i (R and R meaning H, alkyl, aryl. or sub stituted aryl) and the othenXsv mean H, alkyl, halogen or. the. groups --C OOH SOH and m and n ,in the presence of an aqueous solution of a bisulfite' salt a naphthalenejcompound'of the general formula mHs a in which at least one Y represents the groups hydroxynaphthalenes' with Journal fiir praktische these statements,

. poundthe best result is obtained? at least oneXmeans. the groups meanlj or 2, by heatingv m hot water which 2-aminonaphthalene Serial No; 407,564; andin GermanylDcceir ber'13} 192 6:-

H or halogen with adiamino compoundofEthe benzene series'being substituted or not, As a diamino compound of the' benzene series we may use for instance ortho-*;;meta-,; or:- paradiami-nes which the nucleus by halogen, alkylor thegroups COOH or SO H'. Furthermorawegmayf use diarninobenz'enes' substituted in' .one amino group to'form for instance amino-m monosor diallzyl-ror aryl-amino benzene; or famine-4:-hydroxydiphenylamine' or 4-45 5 diaminodiphenylamineQ-sulfonic :acidJ The yields are very satisfactory and the 'prod nets are in apure'state if thereactionisca'rried out under suitable conditions, namely-1 whilst stirring intensively and at temperatures not considerably below theboili'ngpointof the mixture to not considerably above 150 C. When carrying out the reaction above. the boiling point of the reaction mixture-a closed vessel must'be used; inathis case the resulting pressure is' a function from the temperatureapplied; and' from' tlltenSlOIrOifi the reacting liquid. The treating:of' the rea c iz. tion"IniXture atthetemperatures-given abovei is continued until a test proves that un changed naphthalene compound applied as starting. materialris no longer.present..- It is further of an advantage for obtaining a. good yield that the amino benzene compound may be substituted in VIRCK, or nEssAu IN NHAIJT, ER ANY,- Jessi(an ons:v inc, or NEW Yonx, 1v. A CORPORATION ori 1s used'in an excess above. the theo'retical amount. When-usingl l 501per.cent ofthew- J theoretical amountz of-theamino benzene com; The following examples serve to ill ustratei the invention; 1 y .1 1. 144 parts ofQ-hydroxynapthalene and;

150 parts of 1.2-diaminobenzene are stirred for 40 hours at a temperature of 1 15,120 ,Cl in a closed enamelled vessel with 4000 partsof a, solution o'ffsodium bisulfite; of 19 B6. 1 strength. After cooling to C. the

product of the reaction is separated from the? aqueous. solution and purified; by dissolving} contains hydrochloric the fminophenyl) hydrochloride is 'sep alittle needles? *B 'y ad 1 acid; After cooling rated inthe jform of dition of a" solution- 0f sodiumcarbonat'e the l V ree base is obtaineds Becrys'talliz dfrom dilute alcohol it melts at 9697 C. From an aqueous solution containing hydrochloric acid it is absorbed by animal fibers on which reddish brown shades are obtained by x a treatment with an oxidizing agent.

2. 144parts of 2-hydroxynaphthalene and 130 parts of 1.3-diaminobenzene are heated to the boiling point for 80 hours whilst stirring with 4000 bisulfite of 19 B. strength in a leaded or enamelled vessel provided with a stirrer and a reflux apparatus.- tion is separated from tion ;v-it may be purified by treating with hot water to which some sodium hydroxide solution is added. It may be'recrystallized from a dilute solution of hydrochloric acid.

3. 137 parts of 1.4-diaminobenzene and 1 14 parts of 2-hydroxynapthalene are boiled for 90100 hours whilst stirring with 4000 parts of a solution of sodium bisulfite of 20 B. strength in a leaded or enamelled vessel provided with a stirrer, a heating device and a reflux apparatus. After cooling to 70 C.the (4aminophenyl) 2-aminonapthalene thus obtained is filtered, pressed and well washed with warm water.

-When treating I the l-hydroxynapthalene under the same conditions the M-aminophenyl)-1-aminonaphthalene is obtained.

4. In a leaded or enamelled vessel provided with a stirrer and a reflux apparatus 288' 400 parts of 4- parts of l-aminonapthalene, amino- 1-hydroxydiphenylamine and 7000 arts of a solution of sodium bisulfite of about 20 B. strength are boiled whilst stirring until after about 120 hours only small quantities of the unchanged starting materials are present. After cooling to -80 C. the product of reaction is separated by filtration, pressed and digested with a very dilute solution of hydrochloric acid and then with hot water to remove the unchanged starting materials.

5. In a vessel described in example 3 140 parts of 2-hydroxynaphthalene and 280 parts of 1.4 -diaminodiphenylamine-2-sulfonic acid are boiled with 2000 parts of a solution of sodium bisulfite of 36 B. strength and 2000 parts of water for 50-70 hours whilst stirring. The product of condensation is separated by addition of an inorganic acid. It is the. l-(B-naphthylamino)-4-aminodiphenylamine sulfonic acid whichis purified by dissolving in a dilute solution of sodium carbonate and reseparating by addition of an acid. In an aqueoussuspension containing soap it is absorbed by acetate silk which is dyed in blue shades by a subsequent treatment with a weak oxidizing agent.

A 4 (anaphthylamino) 45 aminodiphenylamine-sulfonic acid is obtained when aplying 1,-aminoor l-hydroxynaphtha'lene instead of 2-hydroxynaphthal'ene.

parts of a solution of sodium The product of reacthe hot aqueous solu-' It is obvious to those skilled in the art that our present invention is not limited to the foregoing examples or to the details given therein. Thus for instance, the hydroxynaphthalenes chosen in the examples may be substituted by the corresponding aminonaphthalenes and vice-versa.

Furthermore, other diaminobenzene compounds substituted in one amino group or in the benzene nucleus may be employed or we may use amino or hydroxynapthalene being substituted in the nucleus, for instance by halogen. It may be stated that instead of sodium bisulfite other soluble bisulfite salts may be used. It is advantageous when employing a more dilute solution of soluble bisulfite salt to heat to a higher temperature and when employing a more concentrated solution to heat only nearly-to the boiling point of the reaction mixture. The aminobenzene. compound employed in an excess may be recovered and reused; I V The present application is a continuation in No. 236,358, filed November .28, 1927.

What we claim is part of our 'co-pending application Serial 5o 1. The process which comprises treating, I

while agitating, in the presence of an aqueous solution of a bisulfite salt at a temperature between and 150 C. a naphthalene compound of the general formula 010 5 3, 7 in which at least one Y represents the group -OH or NI-I andthe other Ys represent H or halogen, with a diamino compound of the general formula 2. The process which comprises treating,

while agitating, in the presence of an aqueous wherein n stands for 0,

solution of a bisulfite salt at a temperature between 100 and 150 C. a; naphthalene compound of the general formula V in which at least one'Y'represents the gr -OH or -NH and the other Ys represent H or halogen, with a diamino compound of the benzene series substituted in one amino group by aphenyl radicle.

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3. The process which comprises treating, I while agitating, in thepresence of an aqueous solution of a bisulfite salt at a temperature between 100 and 150 C. a naphthalene compound of the general formula inwhich at least one'Y represents the group X meaning alkyl phenyl which may aqueous solution from which it is not precipi- OH or NH and the other Ys represent H or halogen, with 4.4-diaminodiphenylamine sulfonic acid.

4. As new products the naphthalene derivatives of the general formula OwH1.HN-ONHX,

be substituted by halogen, alkyl, CO()H, or SO H, which products'in the dried state are gray crystalline powders insoluble in water, slightly soluble in benzene, alcohol, ether, and soluble in dilute hydrochloric acid, having in an acid solution an aifinity to animal fibers on which they may be fixed from gray to violet to blue to green to deep black shades fast to milling and tolight when treated with an oxidizing agent.

5. As new products the naphthalene derivatives of the general formula owH1.HN ONHO x,

black shades fast to milling and to light when treated with an oxiding agent.

6. As new products the naphthalene derivatives of the general formula X meaning H, alkyl, NH -OH, halogen, which products in the dry state are gray crystalline powders insoluble in water, slightly soluble in benzene, alcohol, ether, and solu-' ble in dilute hydrochloric acid having in an acid solution an affinity to animal fibers on which they may be fixed from gray to bluish black shades fast to milling and to light when treated with an oxidizing agent.

amino) -4-amino-dipheny1amine sulfonic acid of the formula which is in the dry state a gray crystalline powder being soluble in a weakly alkaline tures.

HEINRICH HEIMANN. .PAUL VIRCK.

7. As new products the naphthalene derivatives of the general formula which products in the dry state are gray crystalline powders being soluble in aweakly al- I kaline aqueous solution from which they are not precipitated by addition of dilute hydrochloric acid if. the solution is hot having in such an acid solutionan aflinity to animal 

